WO2020042079A1

WO2020042079A1 - Process for preparing solketal amine via direct amination

Info

Publication number: WO2020042079A1
Application number: PCT/CN2018/103226
Authority: WO
Inventors: Bright KUSEMA; Stéphane STREIFF; Zhen YAN; Arthur MALHEIRO
Original assignee: Rhodia Operations; Rhodia Poliamida E Especialidades S.A.
Priority date: 2018-08-30
Filing date: 2018-08-30
Publication date: 2020-03-05
Also published as: BR112021003135A8; CN112638890A; BR112021003135A2

Abstract

Disclosed a process for preparing a solketal amine via direct amination. It is possible to obtain solketal amines by very simple procedure with desired characteristics such as simplicity, inexpensiveness, high yield and conversion, as well as low environmental impact.

Description

[Title established by the ISA under Rule 37.2] PROCESS FOR PREPARING SOLKETAL AMINE VIA DIRECT AMINATION

TECHNICAL FIELD

The present invention relates to a process for preparing a solketal amine via direct amination.

BACKGROUD

The preparation of solketal amines is seldom reported in the literature. These reported routes are usually multi-step process and also generate salts or require relatively harsh conditions, making them not viable for industrial application.

Danielmeier, K.; Steckhan, E. Tetrahedron 6 (5) (1995) p. 1181 –1190 described the synthesis of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine, a key intermediate for their work, by multi-step route. First, the protected glyceraldehyde was transformed in situ to an oxime, and then, the last was reduced using LiAlH ₄. Goubert et al. Tetrahedron 63 (2007) p. 8255 –8266 described a multi-step process to obtain 2, 2-dimethyl-1, 3-dioxolan-4-yl) methanamine. For this, triphenylphosphine, phthlimide and diisopropylazodicarboxylate were added a solution of solketal to obtain tosyl solketal as an intermediate. Then, hydrazine monohydrate was added to a suspension of this intermediate to afford the target product. In addition, a multi-step route via 3-amino-propan-1, 2-diol and dimethoxy propane was proposed, but a significant amount of salt is produced as by-product.

Lemaire M. Synthesis 6 (1995) p. 627 –629 proposed the multi-step synthesis of solketal-derived secondary amines, using solketal as starting material. Initially, solketal was converted into its mesylate, this intermediate was reflux with benzylamine in acetonitrile to give the secondary amine. Additionally, this process used unfriendly substances as solvent. Recently, Mbakidi and Sandrine Journal of Molecular Liquids 252 (2018) p. 218 –224 described the preparation of ionic liquids based on solketal amines. To obtain solketal-derived secondary and tertiary amines, a multi-step synthesis was performed through the preparation of tosyl solketal in the first step. After tosylation, amination was performed with a microwaves-assisted substitution with the appropriate amine.

Hamid et al. J. Am. Chem. Soc. 131 (5) (2009) p. 1766 –1774 showed that solketal can be aminated with dimethylamine in 70%yield, using [Ru (p-cymene) Cl ₂] ₂ with the bidentate phosphine dppf ot DPEphos as catalyst.

There is still a need to provide a process prepare solketal amines with desired characteristics such as simplicity, inexpensiveness, high yield and conversion, as well as low environmental impact, which can overcome the drawbacks in prior arts.

DEFINITIONS

For convenience, before further description of the present disclosure, certain terms employed in the specification, and examples are collected here. These definitions should be read in the light of the remainder of the disclosure and understood as by a person of skill in the art. The terms used herein have the meanings recognized and known to those of skill in the art, however, for convenience and completeness, particular terms and their meanings are set forth below.

The articles “a” , “an” and “the” are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article.

The term “and/or” includes the meanings “and” , “or” and also all the other possible combinations of the elements connected to this term.

Throughout the description, including the claims, the term "comprising one" should be understood as being synonymous with the term "comprising at least one" , unless otherwise specified, and "between" should be understood as being inclusive of the limits.

It should be noted that in specifying any range of concentration, any particular upper concentration can be associated with any particular lower concentration.

It is specified that, in the continuation of the description, unless otherwise indicated, the values at the limits are included in the ranges of values which are given.

As used herein, the term "hydrocarbon group" refers to a group which contains carbon and hydrogen bonds. A hydrocarbon group may be linear, branched, or cyclic, and may contain a heteroatom such as oxygen, nitrogen, sulfur, halogen, etc.

As used herein, the term "alkyl" means a saturated hydrocarbon radical, which may be straight, branched or cyclic, such as, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, pentyl, n-hexyl, cyclohexyl.

As used herein, the term "alkenyl" as a group or part of a group denotes an aliphatic hydrocarbon group containing at least one carbon-carbon double bond and which may be straight or branched. The group may contain a plurality of double bonds in the normal chain and the orientation about each is independently E or Z. Exemplary alkenyl groups include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl and nonenyl. The group may be a terminal group or a bridging group.

As used herein, the term "aryl" refers to a monovalent aromatic hydrocarbon group, including bridged ring and/or fused ring systems, containing at least one aromatic ring. Examples of aryl groups include phenyl, naphthyl and the like. The term "arylalkyl" or the term "aralkyl" refers to alkyl substituted with an aryl. The term "arylalkoxy" refers to an alkoxy substituted with aryl.

As used herein, the term "cyclic group" means a closed ring hydrocarbon group that is classified as an alicyclic group, aromatic group, or heterocyclic group. The term "alicyclic group" means a cyclic hydrocarbon group having properties resembling those of aliphatic groups.

As used herein, the term "cycloalkyl" as used herein means cycloalkyl groups containing from 3 to 8 carbon atoms, such as for example cyclohexyl.

The heterocyclic group may also mean a heterocyclic group fused with a benzene-ring wherein the fused rings contain carbon atoms together with 1 or 2 heteroatom’s which are selected from N, O and S.

As used herein, the term "heterocycloalkane" means a saturated heterocycle formally derived from a cycloalkane by replacing one or more carbon atoms with a heteroatom.

As used herein, the terminology " (C _n-C _m) " in reference to an organic group, wherein n and m are each integers, indicates that the group may contain from n carbon atoms to m carbon atoms per group.

As used herein, metals of group IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB are often referred to as transition metals. This group comprises the elements with atomic number 21 to 30 (Sc to Zn) , 39 to 48 (Y to Cd) , 72 to 80 (Hf to Hg) and 104 to 112 (Rf to Cn) .

As used herein, the term “Lanthanides” refer to metals with atomic number 57 to 71.

As used herein, rare earth metal (REM) , as defined by IUPAC, is one of a set of seventeen chemical elements in the periodic table, specifically the fifteen lanthanides, as well as scandium and yttrium. Rare earth elements are cerium (Ce) , dysprosium (Dy) , erbium (Er) , europium (Eu) , gadolinium (Gd) , holmium (Ho) , lanthanum (La) , lutetium (Lu) , neodymium (Nd) , praseodymium (Pr) , promethium (Pm) , samarium (Sm) , scandium (Sc) , terbium (Tb) , thulium (Tm) , ytterbium (Yb) and yttrium (Y) .

DETAILED DESCRIPTION

The present invention relates to a process for producing a solketal amine compound having general formula (I) , said process comprising reacting a compound having general formula (II) with a compound having general formula (III) in the presence of a supported metal catalyst,

R ₃R ₄NH (III)

wherein:

- R ₁ and R ₂, identical to or different from each other, represent hydrogen or a hydrocarbon group,

- R ₃ and R ₄, identical to or different from each other, represent hydrogen or a hydrocarbon group, which is optionally interrupted by one or several heteroatoms and/or which is optionally substituted by one or several functional groups.

Through continuous studies concerning improved process for preparing solketal amines, the applicant has now surprisingly found that it is possible to advantageously obtain solketal amines by very simple procedure. The present invention can overcome all the drawbacks of prior art processes.

R ₁ and R ₂, independently from one another, are chosen in the group consisting of: hydrogen or a linear or branched C ₁-C ₁₂ alkyl, a C ₄-C ₁₂ cycloalkyl and an aryl.

Preferably, R ₁ and R ₂, independently from one another, can be chosen in the group consisting of: hydrogen, methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, tert-butyl, n-pentyl, cyclopentyl, cyclohexyl and phenyl.

R ₃ and R ₄, independently from one another, are notably chosen in the group consisting of: hydrogen or a linear or branched C ₁-C ₁₂ alkyl, a C ₄-C ₁₂ cycloalkyl and an aryl.

Preferred groups for R ₃ or R ₄ may be H or alkyl. More preferred groups for R ₃ or R ₄ may be H or C ₁-C ₅ alkyl.

Preferably, R ₃ and R ₄ are all hydrogen.

One preferred embodiment is when R ₁ and R ₂ of formula (I) are methyl and R ₃ and R ₄ of formula (I) are hydrogen.

In another embodiment, R ₁ of formula (I) is methyl, R ₂ of formula (I) is isobutyl, and R ₃ and R ₄ of formula (I) are hydrogen.

In a third embodiment, R ₁ of formula (I) is methyl, R ₂ of formula (I) is phenyl, and R ₃ and R ₄ of formula (I) are hydrogen.

In a fourth embodiment, R ₁ of formula (I) is isopropyl and R ₂, R ₃ and R ₄ of formula (I) are hydrogen.

Preferably, R ₃ is hydrogen and R ₄ is a linear or branched C ₁-C ₁₂ alkyl, or a C ₄-C ₁₂ cycloalkyl.

Advantageously, the compound of formula (I) can be chosen in the group consisting of: 2, 2-dimethyl-1, 3-dioxolane-4-methanamine, 2, 2-diisobutyl-1, 3-dioxolane-4-methanamine, 2-isobutyl-2-methyl-1, 3-dioxolane-4-methanamine, 2-isopropyl-1, 3-dioxolane-4-methanamine, 2-butyl-2-ethyl-1, 3-dioxolane-4-methanamine, 2-phenyl-1, 3-dioxolane-4-methanamine 2-methyl-2-phenyl-1, 3-dioxolane-4-methanamine and (2- (heptan-3-yl) -1, 3-dioxolan-4-yl) methanamine.

The compound of formula (I) may notably a compound having general formula (IV) :

wherein R ₁ and R ₂ have the same meaning as above defined.

Advantageously, the compound of formula (IV) can be chosen in the group consisting of: bis ( (2, 2-dimethyl-1, 3-dioxolan-4-yl) methyl) amine, bis ( (2, 2-diisobutyl -1, 3-dioxolan-4-yl) methyl) amine, bis ( (2-isobutyl-2-methyl -1, 3-dioxolan-4-yl) methyl) amine, bis ( (2-isopropyl -1, 3-dioxolan-4-yl) methyl) amine, bis ( (2-butyl-2-ethyl-1, 3-dioxolan-4-yl) methyl) amine, bis ( (2-phenyl-1, 3- dioxolan-4-yl) methyl) amine, bis ( (2-methyl-2-phenyl -1, 3-dioxolan-4-yl) methyl) amine and bis ( (2- (heptan-3-yl) -1, 3-dioxolan-4-yl) methyl) amine.

One preferred embodiment is when R ₁ and R ₂ of formula (II) are methyl. In this case, the compound is commercially available, for example under the name

SL191 or Solketal. This compound can be synthesized by reaction between glycerol and acetone, under well-known classical conditions.

In another embodiment, R ₁ of formula (II) is methyl, R ₂ of formula (II) is isobutyl. In this case, the compound is commercially available, for example under the name

Clean Plus. This compound can be synthesized by reaction between glycerol and methyl-isobutyl ketone, under well-known classical conditions.

In a third embodiment, R ₁ of formula (II) is methyl, R ₂ of formula (II) is phenyl. In this case, the compound is commercially available, for example under the name

Film HB. This compound can be synthesized by reaction between glycerol and acetophenone, under well-known classical conditions.

In a fourth embodiment, R ₁ of formula (II) is isopropyl and R ₂ of formula (II) is H. In this case, the compound is 2-isobutyl-2-methyl-1, 3-dioxolane-4-methanol. This compound can be synthetized by reaction between glycerol and isobutyraldehyde, under well-known classical conditions.

Advantageously, the compound having general formula (II) is chosen in the group consisting of: 2, 2-dimethyl-1, 3-dioxolane-4-methanol, 2, 2-diisobutyl-1, 3-dioxolane-4-methanol, 2-isobutyl-2-methyl-1, 3-dioxolane-4-methanol, 2-isopropyl-1, 3-dioxolane-4-methanol, 2-butyl-2-ethyl-1, 3-dioxolane-4-methanol, 2-phenyl-1, 3-dioxolane-4-methanol and 2-methyl-2-phenyl-1, 3-dioxolane-4-methanol and (2- (heptan-3-yl) -1, 3-dioxolan-4-yl) methanol.

R ₃ and R ₄ of formula (III) have the same meaning as above defined.

Advantageously, the compound having general formula (III) is chosen in the group consisting of: NH ₃, (CH ₃) ₂NH, (C ₂H ₅) ₂NH, (C ₃H ₇) ₂NH, (C ₄H ₉) ₂NH and (C ₅H ₁₁) ₂NH.

The compound having general formula (III) can even be chosen in the group consisting of: 2, 2-dimethyl-1, 3-dioxolane-4-methanamine, 2, 2-diisobutyl-1, 3-dioxolane-4-methanamine, 2-isobutyl-2-methyl-1, 3-dioxolane-4-methanamine, 2-isopropyl-1, 3-dioxolane-4-methanamine, 2-butyl-2-ethyl-1, 3-dioxolane-4-methanamine, 2-phenyl-1, 3-dioxolane-4-methanamine 2-methyl-2-phenyl-1, 3-dioxolane-4-methanamine and (2- (heptan-3-yl) -1, 3-dioxolan-4-yl) methanamine.

The molar ratio of the compound having general formula (II) to the compound having general formula (III) at the beginning of the reaction is from 1: 1 to 1: 50.

When NH ₃ is employed as reactant, the molar ratio of the compound having general formula (II) to ammonia at the beginning of the reaction is from 1: 1 to 1: 30 in one embodiment.

The supported metal catalyst according to the present invention comprises at least one metal in elemental form and/or at least one metal compound of at least one metal element.

The metal in elemental form or the metal comprised in the metal compound can be chosen in the group consisting of: (i) elements of group IA except hydrogen, (ii) elements of group IIA, (iii) elements of group IIIA, (iv) elements of group IVA except carbon, (v) arsenic, antimony, bismuth, tellurium, polonium and astatine, (vi) elements of groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB, (vii) lanthanides, (viii) actinides and (ix) mixtures thereof.

Preferably, the metal in elemental form or the metal comprised in the metal compound is chosen in the group consisting of nickel, cobalt, copper, tin, aluminum, chromium, platinum, palladium, rhodium, ruthenium, iridium, silver, gold, cerium, bismuth, rhenium, and any combination thereof, more preferably chosen in the group consisting of nickel, cobalt, ruthenium and mixtures thereof and most preferably nickel.

In some embodiments, the supported metal catalyst comprises one and only one metal in elemental form.

In some embodiments, the supported metal catalyst comprises at least two metals in elemental form.

Metal compound comprised in supported metal catalyst is preferably chosen in the group consisting of: metal oxides, salts of metal and any combination thereof. Said salts could be chosen in the group consisting of halide, nitrate, nitrite, carbonate, bicarbonate, sulphate, sulphite, thiosulfate, phosphate, phosphite, hypophosphite, formate, acetate and propionate.

In a particular embodiment, the supported metal catalyst according to the present invention comprises at least one metal in elemental form and at least one metal oxide.

The support to the metal catalyst is not particularly limited. It can notably be a metal oxide chosen in the group consisting of aluminum oxide (Al ₂O ₃) , silicon dioxide (SiO ₂) , titanium oxide (TiO ₂) , zirconium dioxide (ZrO ₂) , calcium oxide (CaO) , magnesium oxide (MgO) , lanthanum oxide (La ₂O ₃) , niobium dioxide (NbO ₂) , cerium oxide (CeO ₂) and mixtures thereof. Preferably, said support is aluminum oxide.

The support can also be a zeolite. Zeolites are substances having a crystalline structure and a unique ability to change ions. People skilled in the art can easily understand how to obtain those zeolites by preparation method reported, such as zeolite L is described in US 4503023 or commercial purchase, such as ZSM available from ZEOLYST.

The support of catalyst can even be Kieselguhr, clay or carbon.

The loading of the metal in elemental form and/or the metal comprised in the metal compound on the support depends on the metal. For example, the loading of noble metal on the support may be comprised from 0.5 wt%to 20 wt%based on total weight of supported metal catalyst and preferably from 2wt%to 10 wt%. The loading of base metal on the support may be comprised from 2 wt%to 50 wt%based on total weight of supported metal catalyst and preferably from 5 wt%to 20 wt%.

As used herein, the noble metals are metals that are normally valuable and resistant to corrosion and oxidation in moist air. Examples of noble metal are ruthenium, rhodium, palladium, silver, osmium, iridium, platinum and gold.

As opposed to a noble metal, base metal according to the present invention refers to relatively inexpensive and common metals, which can be nickel, copper, lead, zinc, iron, aluminium, tin, tungsten, molybdenum, tantalum, cobalt, bismuth, cadmium, titanium, zirconium, antimony, manganese, beryllium, chromium, germanium, vanadium, gallium, hafnium, indium, niobium, rhenium and thallium.

The supported catalyst includes those commercially available under the trade designations “PRICAT CU 60/35” , “T-4419” , “PRICAT Ni 52/35” , “PRICAT Ni 62/15” , “T-8031” , “C18-HA” , “PRICAT Ni 20/15” , “T-4466” , “T-4489” , “HTC Ni 500” , “Ni 1404 T3/16 RS” , “Ni 5132 RS” (available from Johnson Matthey, Sud-Chemie or BASF) .

The catalyst according to the present invention could be prepared by well-known ways, such as incipient wetness impregnation (IWI) method.

Incipient wetness impregnation, also called capillary impregnation or dry impregnation, is a commonly used technique for the synthesis of heterogeneous catalysts. Typically, the active metal precursor is dissolved in an aqueous or organic solution. Then the metal-containing solution is added to a catalyst support containing the same pore volume as the volume of the solution that was added. Solution added in excess of the support pore volume causes the solution transport to change from a capillary action process to a diffusion process, which is much slower. The catalyst can then be dried and calcined to drive off the volatile components within the solution, depositing the metal on the catalyst surface. The maximum loading is limited by the solubility of the precursor in the solution. The concentration profile of the impregnated compound depends on the mass transfer conditions within the pores during impregnation and drying.

The weight ratio of catalyst to the compound having general formula (II) at the beginning of the reaction is from 1: 1 to 1: 50.

The reaction may be performed in the absence or in the presence of a solvent. Preferably, the reaction is performed without using any solvent.

The solvent is typically chosen based on its ability to dissolve the reactants. It may be protic, aprotic or a combination of protic and aprotic solvents. Exemplary solvents include toluene, octane, o-xylene, m-xylene, p-xylene, benzene, tetrahydrofuran, n-butanol, t-butanol, 2-methylbutan-2-ol and acetonitrile. Solvents comprising hydroxyl functionalities or amine functionalities may be used as long as the solvent does not participate in the reaction in place of the reactant.

The reactants, with an optional solvent, and the catalyst are typically combined in a reaction vessel and stirred to constitute the reaction mixture. The reaction mixture is typically maintained at the desired reaction temperature under stirring for a time sufficient to form the amines in the desired quantity and yield.

Preferably, the reaction temperature is in a range of 150 to 200℃.

Preferably, the reaction time is in a range of 10 to 20 hours.

According to the present invention, hydrogen can be optionally introduced into the reaction medium in this invention.

It can be understood by the skilled person that when NH ₃ is used as a reactant, it can be introduced in the form of liquid or gas and preferably in the form of gas.

When the reaction is performed in liquid phase, NH ₃ and H ₂ might be mixed and introduced into reaction medium in one embodiment. In gas phase, the reaction may be performed under a pressure comprised between 1 and 100 bars, preferably between 1 and 20 bars.

The reaction may be carried out in the presence of air but preferably with an inert atmosphere, such as N ₂, Ar, or CO ₂. Those atmospheres may be introduced to the reaction mixture solely or in a form of mixture with NH ₃ and/or H ₂.

When catalytic reaction is carried out in a fixed bed reactor, the weight hourly space velocity of the reaction according to the present invention is from 1.0 to 4.0 h ^-1.

As used herein, weight hourly space velocity (hereinafter WHSV) is defined as the weight of feed flowing per unit weight of the catalyst per hour.

The catalyst is typically removed from the reaction mixture using any solid/liquid separation technique such as filtration, centrifugation, and the like or a combination of separation methods. The product may be isolated using standard isolation techniques, such as distillation. The separation of such heterogeneous catalyst is more convenient than homogeneous catalyst used in the prior art.

In addition, the catalyst can be reused. If desired, the catalyst can be regenerated by washing with methanol, water or a combination of water and methanol and subjecting the washed catalyst to a temperature of about 100 ℃ to about 500 ℃ for about 2 to 24 hours in the presence of oxygen.

Advantageously, it has now been surprisingly found that the conversion of the compound having general formula (II) is of at least 50%and the selectivity of the compound having general formula (I) is of at least 50%by using the supported Ni catalyst.

The present invention extends to a composition, which is the reaction mixture of the process according to the present invention, comprising:

-a compound having general formula (II) ,

-a compound having general formula (III) ,

R ₃R ₄NH (III)

and

-a supported metal catalyst,

wherein:

Optionally, the composition can further comprise a solvent, which has the same meaning as above defined.

Optionally, the composition can further comprise hydrogen.

Optionally, the composition can further comprise a solketal amine compound having general formula (I) :

wherein R ₁, R ₂, R ₃ and R ₄ have the same meaning as above defined.

The following examples are included to illustrate embodiments of the invention. Needless to say, the invention is not limited to the described examples.

EXPERIMENTAL PART

Raw materials

γ-Al ₂O ₃ (Puralox SCCa-5/170, 154 m ²/g, SASOL)

Pricat Nickel 52/35 (Johnson Matthey)

Ni (NO ₃) ₂.6H ₂O (Sinopharm)

Co (NO ₃) ₂.6H ₂O (Sinopharm)

Pricat Nickel 52/35 (Johnson Matthey)

2, 2-dimethyl-1, 3-dioxolane-4-methanol (Solvay)

o-xylene (Sigma Aldrich)

Example 1

Catalyst preparation

γ-Al ₂O ₃ (Puralox SCCa-5/170, 154 m ²/g, SASOL) 1g was impregnated by 8 wt%Ni using incipient wetness impregnation method. For this, 0.4350g Ni (NO ₃) ₂.6H ₂O was dissolved in 0.5g H ₂O and the aqueous solution was added dropwise to γ-Al ₂O ₃ while stirring. The mixture was dried at 100℃ overnight and calcined in static air at 400℃ using a heating rate of 5℃/min for 2h.

Example 2

Catalyst preparation

γ-Al ₂O ₃ (Puralox SCCa-5/170, 154 m ²/g, SASOL) 1g was impregnated by 10 wt%Ni using incipient wetness impregnation method. For this, 0.5550g (Ni (NO ₃) ₂.6H ₂O was dissolved in 0.5g H ₂O and the aqueous solution was added dropwise to γ-Al ₂O ₃ while stirring. The mixture was dried at 100℃ overnight and calcined in static air at 400℃ using a heating rate of 5℃/min for 2h.

Example 3

Catalyst preparation

γ-Al ₂O ₃ (Puralox SCCa-5/170, 154 m ²/g, SASOL) 1g was impregnated by 15 wt%Ni using incipient wetness impregnation method. For this, 0.8800g (Ni (NO ₃) ₂.6H ₂O was dissolved in 0.5g H ₂O and the aqueous solution was added dropwise to γ-Al ₂O ₃ while stirring. The mixture was dried at 100℃ overnight and calcined in static air at 400℃ using a heating rate of 5℃/min for 2h.

Example 4

Catalyst preparation

γ-Al ₂O ₃ (Puralox SCCa-5/170, 154 m ²/g, SASOL) 1g was impregnated by 10 wt%Co using incipient wetness impregnation method. For this, 0.5550g (Co (NO ₃) ₂.6H ₂O was dissolved in 0.5g H ₂O and the aqueous solution was added dropwise to γ-Al ₂O ₃ while stirring. The mixture was dried at 100℃ overnight and calcined in static air at 400℃ using a heating rate of 5℃/min for 2h.

Example 5

Synthesis of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine

The catalytic reaction in the liquid phase was carried out in a sealed 30 mL autoclave. 75mg of 8 wt. %Ni/Al ₂O ₃ catalyst was pre-reduced at 400℃ using a heating rate of 5℃/min for 1 h by 40mL/min H ₂.1.5 mmol 2, 2-dimethyl-1, 3-dioxolane-4-methanol in 3mL o-xylene, 1 bar H ₂ and 15mmol NH ₃ were charged into the reactor. The temperature was raised to 180℃ and kept for 18h. 76%conversion of 2, 2-dimethyl-1, 3-dioxolane-4-methanol, 70%selectivity of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine and 22%selectivity of bis ( (2, 2-dimethyl-1, 3-dioxolan-4-yl) methyl) amine were obtained.

Example 6

Synthesis of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine

The catalytic reaction in the liquid phase was carried out in a sealed 30 mL autoclave. 95mg of 10 wt. %Ni/Al ₂O ₃ catalyst was pre-reduced at 400℃ using a heating rate of 5℃/min for 1 h by 40mL/min H ₂.1.5 mmol 2, 2-dimethyl-1, 3-dioxolane-4-methanol in 3mL o-xylene, 1 bar H ₂ and 15mmol NH ₃ were charged into the reactor. The temperature was raised to 180℃ and kept for 18h. 72%conversion of 2, 2-dimethyl-1, 3-dioxolane-4-methanol and 94%selectivity of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine and 5%selectivity of bis ( (2, 2-dimethyl-1, 3-dioxolan-4-yl) methyl) amine were obtained.

Example 7

Synthesis of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine

The catalytic reaction in the liquid phase was carried out in a sealed 30 mL autoclave. 75mg of 15 wt. %Ni/Al ₂O ₃ catalyst was pre-reduced at 400℃ using a heating rate of 5℃/min for 1 h by 40mL/min H ₂.1.5 mmol 2, 2-dimethyl-1, 3-dioxolane-4-methanol in 3mL o-xylene, 1 bar H ₂ and 15mmol NH ₃ were charged into the reactor. The temperature was raised to 180℃ and kept for 18h. 68%conversion of 2, 2-dimethyl-1, 3-dioxolane-4-methanol, 73%selectivity of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine and 18%bis ( (2, 2-dimethyl-1, 3-dioxolan-4-yl) methyl) amine were obtained.

Example 8

Synthesis of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine

The catalytic reaction in the liquid phase was carried out in a sealed 30 mL autoclave. 75mg of 10 wt. %Co/Al ₂O ₃ catalyst was pre-reduced at 500℃ using a heating rate of 5℃/min for 1 h by 40mL/min H ₂.1.5 mmol 2, 2-dimethyl-1, 3-dioxolane-4-methanol in 3mL o-xylene, 1 bar H ₂ and 15mmol NH ₃ were charged into the reactor. The temperature was raised to 180℃ and kept for 18h. 17%conversion of 2, 2-dimethyl-1, 3-dioxolane-4-methanol, 69%selectivity of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine and 21%bis ( (2, 2-dimethyl-1, 3-dioxolan-4-yl) methyl) amine were obtained.

Example 9

Synthesis of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine

The catalytic reaction in the liquid phase was carried out in a sealed 30 mL autoclave. 75mg of Pricat Nickel 52/35 catalyst (Jonhson Matthey) was activated at 200℃ using a heating rate of 5℃/min for 1 h by 40mL/min H ₂.15 mmol 2, 2-dimethyl-1, 3-dioxolane-4-methanol, 1 bar H ₂ and 150mmol NH ₃ were charged into the reactor. The temperature was raised to 180℃ and kept for 18h. 50% conversion of 2, 2-dimethyl-1, 3-dioxolane-4-methanol and 66%selectivity of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine were obtained.

Example 10

Synthesis of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine

The catalytic reaction in the liquid phase was carried out in a sealed 30 mL autoclave. 75mg of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200℃ using a heating rate of 20℃/h for 1 h by 125mL/min H ₂.1.5 mmol 2, 2-dimethyl-1, 3-dioxolane-4-methanol in 3mL o-xylene, 1 bar H ₂ and 15mmol NH ₃ were charged into the reactor. The temperature was raised to 200℃ and kept for 18h. 85%conversion of 2, 2-dimethyl-1, 3-dioxolane-4-methanol, 65%selectivity of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine and 29%bis ( (2, 2-dimethyl-1, 3-dioxolan-4-yl) methyl) amine were obtained.

Example 11

Synthesis of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine

The catalytic reaction in the liquid phase was carried out in a sealed 30 mL autoclave. 75mg of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200℃ using a heating rate of 20℃/h for 1 h by 125mL/min H ₂.15 mmol 2, 2-dimethyl-1, 3-dioxolane-4-methanol, 1 bar H ₂ and 150 mmol NH ₃ were charged into the reactor. The temperature was raised to 200℃ and kept for 18h. 50%conversion of 2, 2-dimethyl-1, 3-dioxolane-4-methanol, 65%selectivity of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine and 28%bis ( (2, 2-dimethyl-1, 3-dioxolan-4-yl) methyl) amine were obtained.

Example 12

Synthesis of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine

The catalytic reaction in the liquid phase was carried out in a sealed 100 mL autoclave. 1.0g of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200℃ using a heating rate of 20℃/h for 1 h by 125mL/min H ₂.24 mmol 2, 2-dimethyl-1, 3-dioxolane-4-methanol in 50mL o-xylene, 1 bar H ₂ and 180 mmol NH ₃ were charged into the reactor. The temperature was raised to 180℃ and kept for 18h. 63%conversion of 2, 2-dimethyl-1, 3-dioxolane-4-methanol, 96%selectivity of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine and 3%bis ( (2, 2-dimethyl-1, 3-dioxolan-4-yl) methyl) amine were obtained.

Example 13

Synthesis of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine

The catalytic reaction in the gas phase was carried out in a fixed bed reactor.

500mg of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200℃ using a heating rate of 20℃/h for 1 h by 125mL/min H ₂. The temperature of the reactor was kept at 200℃ and 1bar total pressure during the reaction. 1.8 mL/h 2, 2-dimethyl-1, 3-dioxolane-4-methanol, the reactant molar ratio of 2, 2-dimethyl-1, 3-dioxolane-4-methanol: H ₂: NH ₃ = 1: 5: 30 and WHSV 3.8 h ^-1 was used. 54%conversion of 2, 2-dimethyl-1, 3-dioxolane-4-methanol, 75%selectivity of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine were obtained.

Example 14

Synthesis of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine

The catalytic reaction in the gas phase was carried out in a fixed bed reactor.

500mg of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200℃ using a heating rate of 20℃/h for 1 h by 125mL/min H ₂. The temperature of the reactor was kept at 200℃ and 1bar total pressure during the reaction. 1.8 mL/h 2, 2-dimethyl-1, 3-dioxolane-4-methanol, the reactant molar ratio of 2, 2-dimethyl-1, 3-dioxolane-4-methanol: H ₂: NH ₃ = 1: 5: 30 and WHSV (weight hourly space velosity) 2.6 h ^-1 was used. 70%conversion of 2, 2-dimethyl-1, 3-dioxolane-4-methanol and 78%selectivity of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine were obtained.

Example 15

Synthesis of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine

The catalytic reaction in the gas phase was carried out in a fixed bed reactor.

500mg of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200℃ using a heating rate of 20℃/h for 1 h by 125mL/min H ₂. The temperature of the reactor was kept at 200℃ and 1bar total pressure during the reaction. 1.8 mL/h 2, 2-dimethyl-1, 3-dioxolane-4-methanol, the reactant molar ratio of 2, 2-dimethyl-1, 3-dioxolane-4-methanol: H ₂: NH ₃ = 1: 5: 30 and WHSV 1.3 h ^-1 was used. 80%conversion of 2, 2-dimethyl-1, 3-dioxolane-4-methanol and 73%selectivity of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine were obtained.

Example 16

Synthesis of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine

The catalytic reaction in the gas phase was carried out in a fixed bed reactor.

500mg of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200℃ using a heating rate of 20℃/h for 1 h by 125mL/min H ₂. The temperature of the reactor was kept at 200℃ and 1bar total pressure during the reaction. 1.8 mL/h 2, 2-dimethyl-1, 3-dioxolane-4-methanol, the reactant molar ratio of 2, 2-dimethyl-1, 3-dioxolane-4-methanol: H ₂: NH ₃ = 1: 5: 5 and WHSV 1.3 h ^-1 was used. 82% conversion of 2, 2-dimethyl-1, 3-dioxolane-4-methanol and 53%selectivity of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine were obtained.

Example 17

Synthesis of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine

The catalytic reaction in the gas phase was carried out in a fixed bed reactor.

500mg of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200℃ using a heating rate of 20℃/h for 1 h by 125mL/min H ₂. The temperature of the reactor was kept at 200℃ and 1bar total pressure during the reaction. 1.8 mL/h 2, 2-dimethyl-1, 3-dioxolane-4-methanol, the reactant molar ratio of 2, 2-dimethyl-1, 3-dioxolane-4-methanol: H ₂: NH ₃ = 1: 5: 15 and WHSV 1.3 h ^-1 was used. 89%conversion of 2, 2-dimethyl-1, 3-dioxolane-4-methanol and 60%selectivity of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine were obtained.

Example 18

Synthesis of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine

The catalytic reaction in the gas phase was carried out in a fixed bed reactor.

500mg of Pricat Nickel 52/35 catalyst (Johnson Matthey) was activated at 200℃ using a heating rate of 20℃/h for 1 h by 125mL/min H ₂. The temperature of the reactor was kept at 200℃ and 1bar total pressure during the reaction. 1.8 mL/h 2, 2-dimethyl-1, 3-dioxolane-4-methanol, the reactant molar ratio of 2, 2-dimethyl-1, 3-dioxolane-4-methanol: H ₂: NH ₃ = 1: 5: 30 and WHSV 1.3 h ^-1 was used. 81%conversion of 2, 2-dimethyl-1, 3-dioxolane-4-methanol and 70%selectivity of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine were obtained.

Claims

A process for producing a solketal amine compound having general formula (I) , said process comprising reacting a compound having general formula (II) with a compound having general formula (III) in the presence of a supported metal catalyst,

wherein:

- R ₁ and R ₂, identical to or different from each other, represent hydrogen or a hydrocarbon group,

- R ₃ and R ₄, identical to or different from each other, represent hydrogen or a hydrocarbon group, which is optionally interrupted by one or several heteroatoms and/or which is optionally substituted by one or several functional groups.
The process according to claim 1, wherein the supported metal catalyst comprises at least one metal in elemental form and/or at least one metal compound of at least one metal element.
The process according to claim 2, wherein the metal in elemental form or the metal comprised in the metal compound is chosen in the group consisting of: (i) elements of group IA except hydrogen, (ii) elements of group IIA, (iii) elements of group IIIA, (iv) elements of group IVA except carbon, (v) arsenic, antimony, bismuth, tellurium, polonium and astatine, (vi) elements of groups IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIIIB, (vii) lanthanides, (viii) actinides and (ix) mixtures thereof.
The process according to claim 3, wherein the metal in elemental form or the metal comprised in the metal compound is chosen in the group consisting of: nickel, cobalt, copper, tin, aluminum, chromium, platinum, palladium, rhodium, ruthenium, iridium, silver, gold, cerium, bismuth, rhenium and mixtures thereof.
The process according to claim 4, wherein the metal in elemental form or the metal comprised in the metal compound is chosen in the group consisting of: nickel, cobalt, ruthenium and mixtures thereof.
The process according to any one of claims 1 to 5, wherein the support of the catalyst is a metal oxide chosen in the group consisting of aluminum oxide (Al ₂O ₃) , silicon dioxide (SiO ₂) , titanium oxide (TiO ₂) , zirconium dioxide (ZrO ₂) , calcium oxide (CaO) , magnesium oxide (MgO) , lanthanum oxide (La ₂O ₃) , niobium dioxide (NbO ₂) , cerium oxide (CeO ₂) and mixtures thereof.
The process according to any one of claims 1 to 5, wherein the support of the catalyst is chosen in the group consisting of zeolite Kieselguhr, clay and carbon.
The process according to any one of claims 1 to 7, wherein R ₁ and R ₂, independently from one another, are chosen in the group consisting of hydrogen, a linear or branched C ₁-C ₁₂ alkyl, a C ₄-C ₁₂ cycloalkyl and an aryl.
The process according to any one of claims 1 to 8, wherein R ₁ and R ₂, independently from one another, are chosen in the group consisting of hydrogen, methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, tert-butyl, n-pentyl, cyclopentyl, cyclohexyl and phenyl.
The process according to any one of claims 1 to 9, wherein R ₃ and R ₄, independently from one another, are chosen in the group consisting of hydrogen, a linear or branched C ₁-C ₁₂ alkyl, a C ₄-C ₁₂ cycloalkyl and an aryl.
The process according to any one of claims 1 to 10, wherein the solketal amine compound having general formula (I) is chosen in the group consisting of 2, 2-dimethyl-1, 3-dioxolane-4-methanamine, 2, 2-diisobutyl-1, 3-dioxolane-4-methanamine, 2-isobutyl-2-methyl-1, 3-dioxolane-4-methanamine, 2-isopropyl-1, 3-dioxolane-4-methanamine, 2-butyl-2-ethyl-1, 3-dioxolane-4-methanamine, 2-phenyl-1, 3-dioxolane-4-methanamine 2-methyl-2-phenyl-1, 3-dioxolane-4-methanamine and (2- (heptan-3-yl) -1, 3-dioxolan-4-yl) methanamine.
The process according to any one of claims 1 to 10, wherein the solketal amine having general formula (I) is a compound having general formula (IV) :

wherein R ₁ and R ₂, identical to or different from each other, represent hydrogen or a hydrocarbon group.
The process according to claim 12, wherein the solketal amine compound having general formula (IV) is chosen in the group consisting of bis ( (2, 2-dimethyl-1, 3-dioxolan-4-yl) methyl) amine, bis ( (2, 2-diisobutyl -1, 3-dioxolan-4-yl) methyl) amine, bis ( (2-isobutyl-2-methyl -1, 3-dioxolan-4-yl) methyl) amine, bis ( (2-isopropyl -1, 3-dioxolan-4-yl) methyl) amine, bis ( (2-butyl-2-ethyl-1, 3-dioxolan-4-yl) methyl) amine, bis ( (2-phenyl-1, 3-dioxolan-4-yl) methyl) amine, bis ( (2-methyl-2-phenyl -1, 3-dioxolan-4-yl) methyl) amine, and bis ( (2- (heptan-3-yl) -1, 3-dioxolan-4-yl) methyl) amine.
The process according to any one of claims 1 to 13, wherein the compound having general formula (II) is chosen in the group consisting of 2, 2-dimethyl-1, 3-dioxolane-4-methanol, 2, 2-diisobutyl-1, 3-dioxolane-4-methanol, 2-isobutyl-2-methyl-1, 3-dioxolane-4-methanol, 2-isopropyl-1, 3-dioxolane-4-methanol, 2-butyl-2-ethyl-1, 3-dioxolane-4-methanol, 2-phenyl-1, 3-dioxolane-4-methanol and 2-methyl-2-phenyl-1, 3-dioxolane-4-methanol and (2- (heptan-3-yl) -1, 3-dioxolan-4-yl) methanol.
The process according to any one of claims 1 to 14, wherein the compound having general formula (III) is chosen in the group consisting of: NH ₃, (CH ₃) ₂NH, (C ₂H ₅) ₂NH, (C ₃H ₇) ₂NH, (C ₄H ₉) ₂NH and (C ₅H ₁₁) ₂NH.
The process according to any one of claims 1 to 14, wherein the compound having general formula (III) is chosen in the group consisting of: 2, 2-dimethyl-1, 3-dioxolane-4-methanamine, 2, 2-diisobutyl-1, 3-dioxolane-4-methanamine, 2-isobutyl-2-methyl-1, 3-dioxolane-4-methanamine, 2-isopropyl-1, 3-dioxolane-4-methanamine, 2-butyl-2-ethyl-1, 3-dioxolane-4-methanamine, 2-phenyl-1, 3-dioxolane-4-methanamine 2-methyl-2-phenyl-1, 3-dioxolane-4-methanamine and (2- (heptan-3-yl) -1, 3-dioxolan-4-yl) methanamine.
The process according to any one of claims 1 to 16, wherein the molar ratio of the compound having general formula (II) to the compound having general formula (III) at the beginning of the reaction is from 1: 1 to 1: 50.
The process according to any one of claims 1 to 17, wherein the weight ratio of catalyst to the compound having general formula (II) at the beginning of the reaction is from 1: 1 to 1: 50.
The process according to any one of claims 1 to 18, wherein the reaction is performed in the presence of a solvent, which is chosen in the group consisting of toluene, octane, o-xylene, m-xylene, p-xylene, benzene, tetrahydrofuran, n-butanol, t-butanol, 2-methylbutan-2-ol and acetonitrile.
A composition comprising:

‐ a compound having general formula (II) ,

‐ a compound having general formula (III) ,

R ₃R ₄NH (III)

and

‐ a supported metal catalyst,

wherein:

‐ R ₁ and R ₂, identical to or different from each other, represent a hydrocarbon group,

‐ R ₃ and R ₄, identical to or different from each other, represent hydrogen or a hydrocarbon group, which is optionally interrupted by one or several heteroatoms and/or which is optionally substituted by one or several functional groups.
The composition according to claim 20, wherein the composition further comprises hydrogen.
The composition according to claim 20 or 21, wherein the composition further comprises a solvent.